Liquid dishwashing detergent compositions

ABSTRACT

Liquid dishwashing detergent compositions comprising a co-surfactant selected from amine oxides, betaines, branched alkyl carboxylates and non bridged polyhydroxy fatty acid amides. The dishwashing composition further comprises a bridged polyhydroxy fatty acid amide for improved sudsing performance.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to liquid detergent compositions,particularly to dishwashing compositions comprising a bridgedpolyhydroxy fatty acid amide which exhibit improved sudsing.

BACKGROUND OF THE INVENTION

The formulator of a manual dishwashing detergent composition is requiredto formulate compositions which meet a number of consumer relevantperformance demands.

Firstly, such a composition should be effective at removing soils fromdirty "dishes" when used in a manual dishwashing process. The soilsencountered in dishwashing are largely but not exclusively food based.Particularly difficult soils to remove include greasy soils, burnt-orbaked-on soils or those which have been allowed to harden onto the disharticle, as well as non-food soils such as lipstick on the rims ofglasses or nicotine stains.

Once the soils have been removed from the dishes the dishwashingdetergent should act so as to suspend these soils in the wash solutionand thus prevent their redeposition onto the dishes, or onto the surfaceof the sink.

In addition, the manual dishwashing composition should be high sudsingand the sudsing should persist throughout the washing process. This isparticularly important as sudsing is used as an indicator by theconsumer of the performance of the detergent composition. Moreover, theconsumer also uses the sudsing profile as an indicator that the washsolution still contains active detergent ingredients and the consumerusually renews the wash solution when the sudsing subsides. Thus, a lowsudsing formulation will tend to be replaced by the consumer morefrequently than is necessary because of the low sudsing level.

The manual dishwashing composition should also be mild to the skin, andparticularly to the hands and should not cause skin dryness, chapping orroughness. Such skin complaints largely result from the removal ofnatural oils from the skin. Thus, the manual dishwashing compositionshould desirably be effective at removing grease from plates but notnatural oils from the skin.

In order to address the consumer demand for effective removal of soilsfound in a dishwashing load, particularly greasy soils, liquid detergentcompositions may comprise certain co-surfactants such as long chainamine oxides, betaines, non-bridged polyhydroxy fatty acid amides andbranched alkyl carboxylates, which have been found particularlyeffective in the removal of such soils, especially when present in highconcentrations. However, a disadvantage of such compounds is theirtendency to reduce the overall sudsing profile of the detergentcomposition.

Thus, it is an aim of the present invention to formulate a dishwashingcomposition which facilitates the removal of soils, especially oily andgreasy soils and which produces a high and persistent level of sudsing.

It has now been found that this objective can be achieved by theincorporation of certain bridged polyhydroxy fatty acid amides intoliquid dishwashing detergent compositions comprising long chain amineoxides, betaines, polyhydroxyfatty acid amides, alkyl carboxylates ormixtures thereof. Furthermore, an additional advantage of the presentinvention is that the suds level produced by the addition of the bridgedpolyhydroxy fatty acid amides is greater than the sudsing produced byconventional suds boosters such as shorter chain length amine oxides.

Polyhydroxy fatty acid amides have been disclosed as surfactants in theart, see for example U.S. Pat. No. 5,194,639, U.S. Pat. No. 5,174,927and U.S. Pat. No. 5,188,769.

SUMMARY OF THE INVENTION

The present invention is a liquid dishwashing detergent compositioncomprising at least 1% of a surfactant system, said system comprising apolyhydroxy fatty acid amide, characterised in that said systemcomprises

a) a polyhydroxy fatty acid amide according to the formula: ##STR1##

wherein X is a bridging group having from 2 to 200 atoms; Z and Z' arethe same or different alcohol-containing moieties having two or morehydroxyl groups, or one of Z or Z' is hydrogen; and R and R' are thesame or different hydrocarbyl moieties having from 1 to 21 carbon atomsand can be saturated, branched or unsaturated and mixtures thereof and

b) a co-surfactant selected from C₁₆ to C₁₈ amine oxides, C₁₀ --C₁₆branched alkyl carboxylates, C₆ --C₁₈ betaines and non bridgedpolyhydroxy fatty acid amides and mixtures thereof.

All weights, ratios and percentages are given as a % weight of the totalcomposition unless otherwise stated.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is a liquid dishwashing detergent compositioncomprising at least 1%, preferably from 10% to 60%, more preferably from20% to 50% of a surfactant system. According to the present invention,the surfactant system comprises as an essential component aco-surfactant selected from C₁₆ to C₁₈ amine oxides, C₁₀ -C₁₆ branchedalkyl carboxylates C₆ -C₁₈ betaines and non bridged polyhydroxy fattyacid amides and mixtures thereof. Preferably the compositions of thepresent invention comprise from 0.1% to 40%, preferably from 1% to 10%,most preferably from 2% to 8% of said co-surfactant.

Amine oxide surfactant

According to the present invention amine oxides suitable for use hereinhave the formula: ##STR2## wherein R₁ is selected from an alkyl,hydroxyalkyl, acylamidopropyl and alkyl phenyl group, or mixturesthereof, containing from 16 to 18 carbon atoms; and R₂ and R₃ areindependently C₁₋₃ alkyl or C₂₋₃ hydroxyalkyl groups, or a polyethyleneoxide group containing from 1 to 3, preferably 1, ethylene oxide groups.These amine oxide surfactants in particular include C₁₆ -C₁₈ alkyldimethyl amine oxides and C₁₆ -C₁₈ alkoxy ethyl dihydroxyethyl amineoxides.

According to the present invention the compositions comprise from 0.1%to 20%, preferably from 0.5% to 10%, most preferably from 1% to 5% ofsaid amine oxide.

Alkyl carboxylate surfactant

Alkyl carboxylates useful herein are those which contain a carboxyl unitconnected to a secondary carbon. It is to be understood herein that thesecondary carbon can be in a ring structure, e.g. as in p-octyl benzoicacid, or as in alkyl-substituted cyclohexyl carboxylates. Thesesurfactants should contain no ether linkages, no ester linkages and nohydroxyl groups. There should be no nitrogen atoms in the head-group(amphiphilic portion). The alkyl carboxylate surfactants usually contain11-15, preferably from 11 to 13 total carbon atoms, although slightlymore (e.g., up to 16) can be tolerated; e.g. p-octyl benzoic acid.

A highly preferred class of alkylcarboxylates comprises the secondarycarboxyl materials of the formula R³ CH(R⁴)COOM, wherein R³ is CH₃(CH₂)x and R⁴ is CH₃ (CH₂)y, wherein y can be O or an integer from 1 to4, x is an integer from 4 to 10 and the sum of (x+y) is 6-14, preferably7-13, most preferably 8-10.

Another class of alkylcarboxylate soaps useful herein comprises thosecarboxyl compounds wherein the carboxyl substituent is on a ringhydrocarbyl unit, i.e., secondary soaps of the formula R⁵ -R⁶ --COOM,wherein R⁵ is C⁷ -C¹⁰, preferably C⁸ -C⁹, alkyl or alkenyl and R⁶ is aring structure, such as benzene, cyclopentane and cyclohexane. (Note: R⁵can be in the ortho, meta or para position relative to the carboxyl onthe ring.)

A further class of alkyl carboxylates comprises secondary carboxylcompounds of the formula CH₃ (CHR)_(k) --(CH₂)_(m) --(CHR)_(n)--CH(COOM)(CHR)_(o) --(CH₂)_(p) --(CHR)_(q) --CH₃, wherein each R is C₁-C₄ alkyl, wherein k, n, o, q are integers in the range of 0-8, providedthat the total number of carbon atoms (including the carboxylate) is inthe range of 10 to 18.

In each of the above formulas M can be any suitable, especiallywater-solubilizing, counterion, e.g., H, alkali metal, alkaline earthmetal, ammonium, alkanolammonium, di- and tri-alkanolammonium, and C₁-C₅ alkyl substituted ammonium. Sodium is convenient, as isdiethanolammonium.

Preferred alkyl carboxylates for use herein are water-soluble membersselected from the group consisting of the water-soluble salts of2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoicacid, 2-butyl-1-octanoic acid, 2-pentyl-1-heptanoic acid andisopentadecanoic acid.

According to the present invention the compositions comprise from 0.1%to 20%, preferably from 0.5% to 10% of said branched alkyl carboxylate.

Non bridged Polyhydroxy fatty acid amide

According to the present invention the non bridged polyhydroxy fattyacid amides suitable for use herein are according to the formula:##STR3## wherein R₁ is H, a C₁ -C₈ hydrocarbyl, 2-hydroxy ethyl,2-hydroxy propyl or mixtures thereof, preferably a C₁ -C₄ alkyl, morepreferably a C₁ or C₂ alkyl, most preferably a C₁, and R₂ is a C₁ -C₂₁hydrocarbyl, preferably straight chain C₇ -C₁₉ alkyl or alkenyl, mostpreferably straight chain C₁₀ -C₁₈ alkyl or alkenyl or mixtures thereof;and Z is a polyhydrocarbyl having a linear hydrocarbyl chain with atleast 2 hydroxyl groups directly connected to the chain or analkoxylated derivative thereof. Z is preferably derived from a reducingsugar in reductive amination reaction; more preferably Z is a glycityl.Suitable reducing sugars include glucose, fructose, maltose, lactose,galactose, mannose and xylose. As raw materials high dextrose cornsyrup, high fructose corn syrup and high maltose corn syrup can beutilised as well as individual sugars listed above. It should beunderstood that these corn syrups may yield a mixture of sugarcomponents for Z. Z is preferably selected from the group consisting of--CH₂ (CHOH)nCH₂ OH, --CH(CH₂ OH)--(CHOH)n-1-CH₂ OH, or --CH₂ --(CHOH)₂(CHOR')(CHOH)--CH₂ OH and alkoxylated derivatives thereof, wherein n isan integer from 3 to 5 inclusive and R' is hydrogen or a cyclic oraliphatic monosaccharide. Most preferred are the glycityls wherein n is4, particularly CH₂ (CHOH)₄ CH₂ OH.

According to the formula R₁ can be for example, N-methyl , N-ethyl,N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxypropyl. R₅ --CO--N< can be for example cocamide, stearimide, oleamide,lauramide, myristamide, capricamide, palmitamide, talloamide etc. Z canbe 1-deoxyglycityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl,1-deoxygalactityl, 1-doexymannityl, 1-deoxymaltotriotityl, etc.According to the present invention the compositions may comprise from0.1% to 30%, preferably from 1% to 20%, most preferably from 3% to 10%of said polyhydroxy fatty acid amide.

Betaine surfactant

According to the present invention the betaines useful herein are thosecompounds having the formula R(R¹)₂ N⁺ R² COO⁻ wherein R is a C₆ -C₁₈hydrocarbyl group, preferably a C₁₀ -C₁₆ alkyl group or C₁₀₋₁₆ acylamidoalkyl group, each R¹ is typically C₁ -C₃ alkyl, preferably methyl, andR² is a C₁ -C₅ hydrocarbyl group, preferably a C₁ -C₃ alkylene group,more preferably a C₁ -C₂ alkylene group. Examples of suitable betainesinclude coconut acylamidopropyldimethyl betaine; hexadecyl dimethylbetaine; C₁₂₋₁₄ acylamidopropylbetaine; C₈₋₁₄ acylamidohexyldiethylbetaine; 4 C₁₄₋₁₆ acylmethylamidodiethylammonio!-1-carboxybutane; C₁₆₋₁₈acylamidodimethylbetaine; C₁₂₋₁₆ acylamidopentanediethyl-betaine; C₁₂₋₁₆acylmethylamidodimethylbetaine. Preferred betaines are C₁₂₋₁₈dimethyl-ammonio hexanoate and the C₁₀₋₁₈ acylamidopropane (or ethane)dimethyl (or diethyl) betaines.

The complex betaines suitable for use herein have the formula: ##STR4##wherein R is a hydrocarbon group having from 7 to 22 carbon atoms,preferably 12 to 14 carbon atoms, A is the group (C(O)), n is 0 or 1, R₁is hydrogen or a lower alkyl group, x is 2 or 3, y is an integer of 0 to4, Q is the group --R₂ COOM wherein R₂ is an alkylene group having from1 to 6 carbon atoms and M is hydrogen or an ion from the groups alkalimetals, alkaline earth metals, ammonium and substituted ammonium and Bis hydrogen or a group Q as defined.

According to the present invention the composition may comprise from0.1% to 10%, preferably from 0.1% to 5% of said betaines.

According to the present invention the sudsing performance of saidliquid dishwashing detergent composition can be improved by the additionof a bridged polyhydroxy fatty acid amide. The bridged polyhydroxy fattyacid amide has the formula: ##STR5## wherein: X is a bridging grouphaving from about 2 to about 200 atoms; Z and Z' are the same ordifferent alcohol-containing moieties having two or more hydroxyl groups(e.g., glycerol, and units derived from reducing sugars such as glucose,maltose and the like), or either one (but not both) of Z or Z' ishydrogen; and R and R' are the same or different hydrocarbyl moietieshaving from about 1 to about 13 carbon atoms and can be saturated,branched or unsaturated (e.g., oleoyl) and mixtures thereof.

Preferred X groups are selected from substituted or unsubstituted,branched or linear alkyl, ether alkyl, amino alkyl, or amido alkylmoieties having from about 2 to about 15 carbon atoms. Preferred alkylmoieties are unsubstituted, linear alkyl moieties having the formula--(CH₂)_(n) --, wherein n is an integer from 2 to about 15, preferablyfrom 2 to about 10, and most preferably from 2 to about 6; and alsounsubstituted, branched alkyl moieties having from 3 to about 15 carbonatoms, preferably from 3 to about 10 carbon atoms, and most preferablyfrom 3 to about 6 carbon atoms. Most preferred are ethylene andpropylene (branched or linear) alkyl moieties. Also preferred areunsubstituted, branched or linear ether alkyl moieties having theformula --R² --(O--R²)_(m) --, wherein each R² is independently selectedfrom C₂ -C₈ branched or linear alkyl and/or aryl moieties (preferablyethyl, propyl or combinations thereof) and m is an integer from 1 toabout 5. X may also be unsubstituted, branched or linear amino and/oramido alkyl moieties having the formula --R² --(N(R³)--R²)_(m) --,wherein each R² is independently selected from C₂ -C₈ branched or linearalkyl and/or aryl moieties (preferably ethyl, propyl or combinationsthereof), m is an integer from 1 to about 5, and R³ is selected fromhydrogen, C₁ -C₅ alkyl, and --C(O)R⁴ --, wherein R⁴ is C₁ -C₂₁ alkyl,including --C(O)R. The X moiety may be derived from commerciallyavailable amine compounds such as, for example, Jeffamines® (supplied byTexaco) such as JED600, JEDR148, JEDR192, JED230, JED2000, J-D230 andJ-D400.

Preferred X moieties therefore include: --(CH₂)₂ --, --(CH₂)₃ --,--(CH₂)₄ --, --(CH₂)₅ --, --(CH₂)₆ --, --CH₂ CH(CH₃)(CH₂)₃ --, --(CH₂)₂--O--(CH₂)₂ --, --(CH₂)₃ --O--(CH₂)₃ --, --(CH₂)₂ --O--(CH₂)₃ --,--(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --, --(CH₂)₃ --O--(CH₂)₂ --O--(CH₂)₃--, --(CH₂)₂ --O--(CH₂)₃ --O--(CH₂)₂ --, --(CH₂)₂ --NH--(CH₂)₂ --,--(CH₂)₃ --NH--(CH₂)₃ --, --(CH₂)₂ --NH--(CH₂)₃ --, --(CH₂)₂--N(C(O)R)--(CH₂)₂ --, --(CH₂)₃ --N(C(O)R)--(CH₂)₃ --, --(CH₂)₂--N(C(O)R)--(CH₂)₃ --, --(CH₂)₂ --NH(C₆ H₄)NH--(CH₂)₂ --, --(CH₂)₃--NH(C₆ H₄)NH--(CH₂)₃ --, --(CH₂)₂ --NHCH₂ (C₆ H₄)CH₂ NH--(CH₂)₂ --,--(CH₂)₃ --NHCH₂ (C₆ H₄)CH₂ NH--(CH₂)₃ --, etc.

Preferred Z and Z' groups are independently selected frompolyhydroxyhydrocarbyl moieties having a linear hydrocarbyl chain withat least 2 hydroxyls (in the case of glycerol) or at least 3 hydroxyls(in the case of other sugars) directly connected to the chain, or analkoxylated derivative (preferably ethoxylated or propoxylated) thereof.Z and Z' preferably will be derived from a reducing sugar, morepreferably Z and/or Z' is a glycityl moiety. Suitable reducing sugarsinclude glucose, fructose, maltose, lactose, galactose, mannose, andxylose, as well as glyceraldehyde. As raw materials, high dextrose cornsyrup, high fructose corn syrup, and high maltose corn syrup can beutilised as well as the individual sugars listed above. These cornsyrups may yield a mix of sugar components for Z and Z'. It should beunderstood that it is by no means intended to exclude other suitable rawmaterials. Z and/or Z' preferably will be selected from the groupconsisting of --CH₂ --(CHOH)_(p) --CH₂ OH, --CH(CH₂ OH)--(CHOH)_(p-1)--CH₂ OH, --CH₂ --(CHOH)₂ (CHOR¹)(CHOH)--CH₂ OH, where p is an integerfrom 1 to 5, inclusive, and R¹ is H or a cyclic mono- or polysaccharide,and alkoxylated derivatives thereof. Most preferred are glycitylswherein p is 4, particularly --CH₂ --(CHOH)₄ --CH₂ OH.

Preferred R and R' groups are independently selected from C₃ -C₂₁hydrocarbyl moieties, preferably straight or branched chain C₃ -C₁₃alkyl or alkenyl, more preferably straight chain C₅ -C₁₁ alkyl oralkenyl, most preferably straight chain C₅ -C₉ alkyl or alkenyl, ormixtures thereof. R--CO--N< and/or R'--CO--N< can be, for example,cocamide, stearamide, oleamide, lauramide, myristamide, capricamide,palmitamide, tallowamide, etc.

Examples of such compounds therefore include, but are not limited to:

CH₃ (CH₂)₆ C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₂ -- CH₂ (CHOH)₄ CH₂OH!NC(O)(CH₂)₆ CH₃ ;

CH₃ (CH₂)₈ C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₂ -- CH₂ (CHOH)₄ CH₂OH!NC(O)(CH₂)₈ CH₃ ;

CH₃ (CH₂)₁₀ C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₂ -- CH₂ (CHOH)₄ CH₂OH!NC(O)(CH₂)₁₀ CH₃ ;

CH₃ (CH₂)₈ C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --CH₂ (CHOH)₄ CH₂ OH!NC(O)(CH₂)₈ CH₃ ;

CH₃ (CH₂)₈ C(O)N CH₂ (CHOH)₄ CH₂ OH!--CH₂ CH(CH₃)(CH₂)₃ -- CH₂ (CHOH)₄CH₂ OH!NC(O)(CH₂)₈ CH₃ ;

CH₃ (CH₂)₈ C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₃ --O--(CH₂)₂ --O--(CH₂)₃ --CH₂ (CHOH)₄ CH₂ OH!NC(O)(CH₂)₈ CH₃ ;

CH₃ (CH₂)₃ CH(CH₂ CH₃)C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₂ -- CH₂ (CHOH)₄CH₂ OH!NC(O)CH(CH₂ CH₃)(CH₂)₃ CH₃ ;

CH₃ (CH₂)₆ C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₃ --O--(CH₂)₂ --O--(CH₂)₃ --CH₂ (CHOH)₄ CH₂ OH!NC(O)(CH₂)₆ CH₃ ;

CH₃ (CH₂)₄ C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₃ --O--(CH₂)₂ --O--(CH₂)₃ --CH₂ (CHOH)₄ CH₂ OH!NC(O)(CH₂)₈ CH₃ ;

C₆ H₅ C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₃ --O--(CH₂)₂ --O--(CH₂)₃ -- CH₂(CHOH)₄ CH₂ OH!NC(O)C₆ H₅ ;

CH₃ (CH₂)₄ C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₂ -- CH₂ (CHOH)₄ CH₂OH!NC(O)(CH₂)₈ CH₃.

These compounds can be readily synthesised from the following disugardiamines: HN CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₂ -- CH₂ (CHOH)₄ CH₂ OH!NH; HNCH₂ (CHOH)₄ CH₂ OH!--CH₂ CH(CH₃)(CH₂)₃ -- CH₂ (CHOH)₄ CH₂ OH!NH; HN CH₂(CHOH)₄ CH₂ OH!--(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ -- CH₂ (CHOH)₄ CH₂OH!NH; HN CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₃ --O--(CH₂)₂ --O--(CH₂)₃ -- CH₂(CHOH)₄ CH₂ OH!NH; and HN CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₃ -- CH₂ (CHOH)₄ CH₂OH!NH.

The compositions according to the present invention comprise from atleast 0.05%, preferably from 0.1% to 30%, more preferably from 0.5% to20%, most preferably from 1% to 10%, of said bridged polyhydroxy fattyacid amide. According to the present invention the compositionpreferably comprises said bridged polyhydroxy fatty acid amides and saidco-surfactant in a ratio of from 1:50 to 50:1, preferably from 1:10 to10:1, more preferably from 1:5 to 5:1.

According to the present invention the detergent composition comprises asurfactant system, said system may comprise at least one additionalsurfactant (other than a polyhydroxyfatty acid amide (a) and amineoxide, betaine, non bridged polyhydroxyfatty acid amide or branchedalkylcarboxylate (b)), the selected from anionic, nonionic, amphotericand zwiterionic surfactants and mixtures thereof.

Nonionic surfactant

Suitable nonionic detergent surfactants for use herein include nonioniccondensates of alkyl phenols, nonionic ethoxylated alcohols and nonionicfatty acid amides. According to the present invention the compositionsmay comprise from 0% to 30%, preferably from 0.1% to 25%, morepreferably from 0.5% to 20% of said nonionic surfactants.

Nonionic condensates of alkyl phenols

The polyethylene, polypropylene, and polybutylene oxide condensates ofalkyl phenols are suitable for use herein. In general, the polyethyleneoxide condensates are preferred. These compounds include thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to about 12 carbon atoms in either a straight chain orbranched chain configuration with the alkylene oxide.

Nonionic ethoxylated alcohol surfactant

The alkyl ethoxylate condensation products of aliphatic alcohols withfrom about 1 to about 25 moles of ethylene oxide are suitable for useherein. The alkyl chain of the aliphatic alcohol can either be straightor branched, primary or secondary, and generally contains from 6 to 22carbon atoms. Particularly preferred are the condensation products ofalcohols having an alkyl group containing from 8 to 20 carbon atoms withfrom about 2 to about 10 moles of ethylene oxide per mole of alcohol.Most preferred are the condensation products of alcohols having an alkylgroup containing from 8 to 14 carbon atoms with from about 6 to about 10moles of ethylene oxide per mole of alcohol. Examples of commerciallyavailable nonionic surfactants of this type include Tergitol™ 15-S-9(the condensation product of C₁₁ -C₁₅ linear alcohol with 9 molesethylene oxide), Tergitol™ 24-L-6 NMW (the condensation product of C₁₂-C₁₄ primary alcohol with 6 moles ethylene oxide with a narrow molecularweight distribution), both marketed by Union Carbide Corporation;Neodol™ 45-9 (the condensation product of C₁₄ -C₁₅ linear alcohol with 9moles of ethylene oxide), Neodol™ 23-6.5 (the condensation product ofC₁₂ -C₁₃ linear alcohol with 6.54 moles of ethylene oxide), Neodol™ 45-7(the condensation product of C₁₄ -C₁₅ linear alcohol with 7 moles ofethylene oxide), Neodol™ 45-4 (the condensation product of C₁₄ -C₁₅linear alcohol with 4 moles of ethylene oxide), Neodol™23-3 (thecondensation product of C₁₂ -C₁₃ linear alcohol with 3 moles of ethyeneoxide) marketed by Shell Chemical Company, Kyro™ EOBN (the condensationproduct of C₁₃ -C₁₅ alcohol with 9 moles ethylene oxide), marketed byThe Procter & Gamble Company, Dobanol 91 marketed by the Shell ChemicalCompany and Lial 111 marketed by Enichem.

Nonionic EO/PO condensates with propylene glycol

The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol aresuitable for use herein. Examples of compounds of this type includecertain of the commercially-available Pluronic™ surfactants, marketed byBASF.

Nonionic EO condensation products with propylene oxide/ethylene diamineadducts

The condensation products of ethylene oxide with the product resultingfrom the reaction of propylene oxide and ethylenediamine are suitablefor use herein. Examples of this type of nonionic surfactant includecertain of the commercially available Tetronic™ compounds, marketed byBASF.

Alkylpolysaccharide

According to the present invention the composition may comprise as anoptional ingredient, alkylpolysaccharides i.e. nonionicalkylpolysaccharides or the corresponding sulphated polysaccharides andmixtures thereof. Alkylpolysaccharides suitable for use herein aredisclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986,having a hydrophobic group containing from about 6 to about 30 carbonatoms, preferably from about 11 to about 30, more preferably 11 to 16carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilicgroup containing from about 1.0 to about 10, preferably from about 1.0to about 3, most preferably from about 1.3 to about 2.7 saccharideunits. Any reducing saccharide containing 5 or 6 carbon atoms can beused, e.g., glucose, galactose and galactosyl moieties can besubstituted for the glucosyl moieties. (Optionally the hydrophobic groupis attached at the 2-, 3-, 4-, etc. positions thus giving a glucose orgalactose as opposed to a glucoside or galactoside.)

The intersaccharide bonds can be, e.g., between the one position of theadditional saccharide units and the 2-, 3-, 4-, and/or 6-positions onthe preceding saccharide units. Optionally, and less desirably, therecan be a polyalkyleneoxide chain joining the hydrophobic moiety and thepolysaccharide moiety. The preferred alkyleneoxide is ethylene oxide.

Typical hydrophobic groups include alkyl groups, either saturated orunsaturated, branched or unbranched containing from 8 to 18, preferablyfrom 10 to 16, carbon atoms. Preferably, the alkyl group is astraight-chain saturated alkyl group. The alkyl group can contain up toabout 3 hydroxyl groups and/or the polyalkyleneoxide chain can containup to about 10, preferably less than 5, alkyleneoxide moieties. Suitablealkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-,tetra-, penta-, and hexaglucosides, galactoses. Suitable mixturesinclude coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallowalkyl tetra-, penta- and hexaglucosides.

The preferred alkylpolyglycosides have the formula:

    R.sup.2 O(C.sub.n H.sub.2n O)t(glycosyl).sub.x

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18, preferably from 12 to 14, carbonatoms; n is 0-3 preferably 2 to 3, t is from 0 to 10, preferably 0, x isfrom 1.0 to 10, preferably from 1.0 to 3, most preferably from 1.3 to2.7. The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.

According to the present invention the dishwashing compositions comprisefrom 0.5% to 50%, preferably from 1% to 30%, more preferably from 1.5%to 20% of said alkylpolysaccharide surfactant.

Anionic surfactant

Anionic surfactants suitable for use herein may be essentially anyanionic surfactant, including anionic sulphate, sulphonate orcarboxylate surfactant.

Anionic sulphate surfactant

The anionic sulphate surfactant may be any organic sulphate surfactant.It is preferably selected from the group consisting of C₁₀ -C₁₆ alkylsulphate which has been ethoxylated with from about 0.5 to about 20moles of ethylene oxide per molecule, C₉ -C₁₇ acyl-N--(C₁ -C₄ alkyl)glucamine sulphate, C₉ -C₁₇ --N--(C₂ -C₄ hydroxyalkyl) glucaminesulphate, and mixtures thereof, wherein the C₉ -C₁₇ acyl group isderived from coconut or palm kernel oil, as described in U.S. Pat. No.2,717,894. More preferably, the anionic sulphate surfactant is a C₁₀-C₁₆ alkyl sulphate which has been ethoxylated with from about 0.5 toabout 12, moles of ethylene oxide per molecule. The C₁₀ -C₁₆ alcoholitself is commercially available. C₁₂ -C₁₄ alkyl sulphate which has beenethoxylated with from about 3 to about 10 moles of ethylene oxide permolecule is also preferred.

Conventional base-catalysed ethoxylation processes to produce an averagedegree of ethoxylation of 12 result in a distribution of individualethoxylates ranging from 1 to 15 ethoxy groups per mole of alcohol, sothat the desired average can be obtained in a variety of ways. Blendscan be made of material having different degrees of ethoxylation and/ordifferent ethoxylate distributions arising from the specificethoxylation techniques employed and subsequent processing steps such asdistillation. The counterion for the anionic sulphate surfactantcomponent is preferably selected from calcium, sodium, potassium,magnesium, ammonium, or alkanol-ammonium, and mixtures thereof, withcalcium and magnesium being preferred for cleaning and sudsing,respectively.

Anionic alkyl ethoxy carboxylate surfactant

Alkyl ethoxy carboxylates suitable for use herein include those with theformula RO(CH₂ CH₂ O)x CH₂ COO--M⁺ wherein R is a C₁₂ to C₁₆ alkylgroup, x ranges from 0 to 10, and the ethoxylate distribution is suchthat, on a weight basis, the amount of material where x is 0 is lessthan 20%, preferably less than 15%, most preferably less than 10%, andthe amount of material where x is greater than 7, is less than 25%,preferably less than 15%, most preferably less than 10%, the average xis from 2 to 4 when the average R is C₁₃ or less, and the average x isfrom 3 to 6 when the average R is greater than C₁₃, and M is a cation,preferably chosen from alkali metal, alkaline earth metal, ammonium,mono-, di-, and tri-ethanolammonium, most preferably from sodium,potassium, ammonium and mixtures thereof with magnesium ions. Thepreferred alkyl ethoxy carboxylates are those where R is a C₁₂ to C₁₄alkyl group.

Anionic alkyl polyethoxy polycarboxylate surfactant

Alkyl polyethoxy polycarboxylate surfactants suitable for use hereininclude those having the formula: ##STR6## wherein R is a C₆ to C₁₈alkyl group, x is from 1 to 25, R₁ and R₂ are selected from the groupconsisting of hydrogen, methyl acid radical, succinic acid radical,hydroxysuccinic acid radical, and mixtures thereof, wherein at least oneR₁ or R₂ is a succinic acid radical or hydroxysuccinic acid radical, andR₃ is selected from the group consisting of hydrogen, substituted orunsubstituted hydrocarbon having between 1 and 8 carbon atoms, andmixtures thereof

Other anionic surfactants

Other anionic surfactants useful for detersive purposes can also beincluded in the compositions hereof. These can include salts (including,for example, sodium, potassium, ammonium, and substituted ammonium saltssuch as mono-, di- and triethanolamine salts) of soap, fatty oleylglycerol sulphates, alkyl phenol ethylene oxide ether sulphates, alkylphosphates, alkyl succinates and sulphosuccinates, monoesters ofsulphosuccinate (especially saturated and unsaturated C₁₂ -C₁₈monoesters) diesters of sulphosuccinate (especially saturated andunsaturated C₆ -C₁₄ diesters), N-acyl C₆₋₂₀ sarcosinates. Resin acidsand hydrogenated resin acids are also suitable, such as rosin,hydrogenated rosin, and resin acids and hydrogenated resin acids presentin or derived from tall oil. Further examples are given in "SurfaceActive Agents and Detergents" (Vol. I and II by Schwartz, Perry andBerch).

Compositions according to the present invention comprise at least 3%,preferably from 3% to 40%, most preferably from 3% to 30% of saidanionic surfactants.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include the alkylamphocarboxylic acids of the formula: ##STR7## wherein R is a C₈ -C₁₈alkyl group, and R_(i) is of the general formula: ##STR8## wherein R¹ isa (CH₂)_(x) COOM or CH₂ CH₂ OH, and x is 1 or 2 and M is preferablychosen from alkali metal, alkaline earth metal, ammonium, mono-, di-,and tri-ethanolammonium, most preferably from sodium, potassium,ammonium and mixtures thereof with magnesium ions. The preferred R alkylchain length is a C₁₀ to C₁₄ alkyl group. A preferred amphocarboxylicacid is produced from fatty imidazolines wherein the dicarboxylic acidfunctionality of the amphodicarboxylic acid is diacetic acid and/ordipropionic acid. A suitable example of an alkyl amphodicarboxylic acidfor use herein ins the amphoteric surfactant Miranol(TM) C2M Conc.manufactured by Miranol, Inc., Dayton, N.J.

In addition to the C₁₆ to C₁₈ amine oxides of the present invention, thedetergent composition may comprise as optional ingredient other amineoxides according to the formula: ##STR9## wherein R³ is selected from analkyl, hydroxyalkyl, acylamidopropyl and alkyl phenyl group, or mixturesthereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbonatoms; R⁴ is an alkylene or hydroxyalkylene group containing from 2 to 3carbon atoms, preferably 2 carbon atoms, or mixtures thereof; x is from0 to 3, preferably 0; and each R⁵ is an alkyl or hydyroxyalkyl groupcontaining from 1 to 3, preferably from 1 to 2 carbon atoms, or apolyethylene oxide group containing from 1 to 3, preferable 1, ethyleneoxide groups. The R⁵ groups can be attached to each other, e.g., throughan oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀ -C₁₄ alkyldimethyl amine oxides and C₈ -C₁₂ alkoxy ethyl dihydroxyethyl amineoxides. Examples of such materials include diethyldecylamine oxide,bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide,dipropyltetradecylamine oxide, dodecylamidopropyl dimethylamine oxideand dimethyl-2-hydroxyoctadecylamine oxide. Preferred are C₁₀ -C₁₄ alkyldimethylamine oxide, and C₁₀₋₁₄ acylamido alkyl dimethylamine oxide.

According to the present invention the detergent composition maycomprise from 0% to 20%, preferably from 1% to 10% of said amine oxide.

Zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergentcompositions herein.

Sultaines

The sultaines useful in the present invention are those compounds havingthe formula (R(R¹)₂ N⁺ R² SO₃ ⁻ wherein R is a C₆ -C₁₈ hydrocarbylgroup, preferably a C₁₀ -C₁₆ alkyl group, more preferably a C₁₂ -C₁₃alkyl group, each R¹ is typically C₁ -C₃ alkyl, preferably methyl, andR² is a C₁ -C₆ hydrocarbyl group, preferably a C₁ -C₃ alkylene or,preferably, hydroxyalkylene group.

Hydrotropes A hydrotrope is typically added to the compositions of thepresent invention, and may be present at levels of from 0% to 40%,preferably from 1% to 15%, by weight.

Useful hydrotropes include sodium, potassium, calcium and ammonium saltsof xylene sulphonate, toluene sulphonate and cumene sulphonate andmixtures thereof. Other compounds useful as hydrotropes herein includepolycarboxylates and urea. Some polycarboxylates have calcium chelatingproperties as well as hydrotropic properties.

An example of a commercially available alkylpolyethoxy polycarboxylatewhich can be employed herein is POLY-TERGENT C, Olin Corporation,Cheshire, Conn., USA.

Another compound useful as a hydrotrope is alkyl amphodicarboxylic acidof the generic formula: ##STR10## wherein R is a C₈ to C₁₈ alkyl group,x is from 1 to 2, M is preferably chosen from alkali metal, alkalineearth metal, ammonium, mono-, di-, and tri-ethanolammonium, mostpreferably from sodium, potassium, ammonium, and mixtures thereof withmagnesium ions. The preferred alkyl chain length (R) is a C₁₀ to C₁₄alkyl group and the dicarboxylic acid functionally is diacetic acidand/or dipropionic acid.

A suitable example of an alkyl amphodicarboxylic acid is the amphotericsurfactant Miranol R 2CM Conc. manufactured by Miranol, Inc., Dayton,N.J., USA.

Organic solvent

The compositions of the invention will most preferably contain anorganic solvent system present at levels of from 1% to 30% by weight,preferably from 1% to 20% by weight, more preferably form 2% to 15% byweight of the composition. The organic solvent system may be a mono, ormixed solvent system; but is preferably in mixed solvent system.Preferably, at least the major component of the solvent system is of lowvolatility. Suitable organic solvents for use herein have the generalformula: ##STR11## wherein R is an alkyl, alkenyl, or alkyl aryl grouphaving from 1 to 8 carbon atoms, and n is an integer from 1 to 4.Preferably, R is an alkyl group containing 1 to 4 carbon atoms, and n is1 or 2. Especially preferred R groups are n-butyl or isobutyl. Preferredsolvents of this type are 1-n-butoxypropane-2-ol (n=1); and1(2-n-butoxy-1-methylethoxy)propane-2-ol (n=2), and mixtures thereof.

Other solvents useful herein include the water soluble CARBITOL orCELLOSOLVE solvents. These solvents are compounds of the2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived fromethyl, propyl or butyl.

Other suitable solvents are benzyl alcohol, and diols such as2-ethyl-1,3-hexanediol and 2,2,4-trimethl-1,3-pentanediol. The lowmolecular weight, water-soluble, liquid polyethylene glycols are alsosuitable solvents for use herein.

The alkane mono and diols, especially the C₁ -C₆ alkane mono and diolsare suitable for use herein. C₁ -C₄ monohydric alcohols (e.g.: ethanol,propanol, isopropanol, butanol and mixtures thereof) are preferred, withethanol particularly preferred. The C1-C4 dihydric alcohols, includingpropylene glycol, are also preferred.

Thickening agents

The compositions according to the present invention may additionallycomprise thickening agents, such as polyquaternium cellulose cationicpolymer, for example Quatrisoft® available from the AmericholCorporation.

Calcium

Compositions according to the present invention may optionally comprisefrom 0.01% to 3%, more preferably from 0.15% to 0.9% of calcium ions. Ithas been found that the presence of calcium greatly improves thecleaning of greasy soils for compositions containing polyhydroxy fattyacid amide. This is especially true when the compositions are used insoftened water, which contains few divalent ions.

The calcium ions can, for example, be added as a chloride, hydroxide,oxide, formate or acetate, or nitrate salt, xylene sulphonate, cumenesulphonate and toluene sulphonate. If the anionic surfactants are in theacid form, the calcium can be added as a calcium oxide or calciumhydroxide slurry in water to neutralise the acid.

The calcium ions may be present in the compositions as salts. The amountof calcium ions present in compositions of the invention may bedependent upon the amount of total anionic surfactant present herein.The molar ratio of calcium ions to total anionic surfactant ispreferably from 1:0.1 to 1:25 more preferably from 1:2 to 1:10, forcompositions of the invention.

Calcium stabilising agent

In order to provide good product stability, and in particular to preventthe precipitation of insoluble calcium salts malic, maleic or aceticacid, or their salts, or certain lime soap dispersant compounds may beadded to the composition of the present invention comprising calcium.Where calcium is present, malic, maleic or acetic acid, or their saltscan be added at levels of from 0.05% to 10% of the composition and amolar ratio with calcium of from 10:1 to 1:10.

Magnesium

From 0.01% to 3%, most preferably from 0.15% to 2%, by weight, ofmagnesium ions are preferably added to the liquid detergent compositionsof the invention for improved product stability, as well as improvedsudsing.

If the anionic surfactants are in the acid form, then the magnesium canbe added by neutralisation of the acid with a magnesium oxide ormagnesium hydroxide slurry in water. Calcium can be treated similarly.This technique minimises the addition of chloride ions, which reducescorrosive properties. The neutralised surfactant salts and thehydrotrope are then added to the final mixing tank and any optionalingredients are added before adjusting the pH.

pH of the compositions

The compositions according to the present invention formulated for usein manual dishwashing applications are preferably formulated to have apH at 20° C. of from 3 to 12, preferably from 6 to 9, most preferablyfrom 6.5 to 8.5.

In another aspect of the present invention the composition may beformulated for use as in pre-treatment applications whereby thecomposition is applied in essentially the concentrated form onto thedishes. Preferably the composition is allowed to remain on the dishesfor a period of time. Compositions for use in such applicationspreferably have a pH of from 3 to 14, more preferably from 3 to 5 orgreater than 8.

Liquid compositions

According to the present invention the detergent compositions are liquiddetergent compositions. In one preferred embodiment of the presentinvention the compositions are high active formulations such that saidcompositions comprise 75% to 50% by weight, preferably from 70% to 55%by weight, most preferably from 65% to 55% by weight of a liquidcarrier, e.g., water, preferably a mixture of water and a C1-C4monohydric alcohol (e.g., ethanol, propanol, isopropanol, butanol, andmixtures thereof), with ethanol being the preferred monohydric alcoholor a mixture of water and C₁ -C₄ dihydric alcohol (e.g.: propyleneglycol). In another preferred embodiment of the present invention thedetergent composition may be in a concentrated form, such that thecomposition is diluted in water prior to usage.

The bridged poly hydroxy fatty acid amides of the present invention maybe prepared by the following method.

EXAMPLE I

Step 1: Reductive Amination

Preparation of HN CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₂ CH₂ (CHOH)₄ CH₂ OH!NH

About 375 g (about 20 wt % based on amount of glucose used) of Raney Ni(Grace Raney Nickel 4200) is contained in a 2 gallon reactor (316stainless steel baffled autoclave with DISPERSIMAX hollow shaftmulti-blade impeller) pressurized to about 300 psig with hydrogen atroom temperature. The nickel bed is covered with water taking up about10% of the reactor volume. This is the first reductive amination run onthe present load of nickel catalyst. 606.53 g of 50 wt % ethylenediaminesolution in water (5.05 moles, 1.00 mole equiv. of ethylenediamine) ismaintained in a separate reservoir which is in closed communication withthe reactor. The reservoir is pressurized to about 100 psig withnitrogen. 3636.36 g of 55 wt % D-glucose solution in water (11.1 moles,2.20 mole equiv. of glucose) is maintained in a second separatereservoir which is also in closed communication with the reactor and isalso pressurized to about 100 psig with nitrogen.

The ethylenediamine is loaded into the reactor from the reservoir usinga high pressure pump. Once all the ethylenediamine is loaded into thereactor, stirring is begun and the reactor heated to 50 deg. C andpressurized to about 500 psig hydrogen.

The glucose solution is then loaded into the reactor from the reservoirusing a high pressure pump similar to the amine pump above. However, thepumping rate on the glucose pump can be varied and on this particularrun, it is set to load the glucose in about 10 minutes. Once all theglucose is loaded into the reactor, the pressure is boosted to about1300 psig hydrogen and the temperature raised to 60 deg. C for about 1hour. The temperature is then raised to 70 deg. C for 10 minutes, 80deg. C for 10 minutes, 100 deg. C for 10 minutes, and finally 120 deg. Cfor 5 minutes, while maintaining hydrogen pressure between 1300-1500psig.

The reactor is then cooled to 70 deg. C and the reaction solutionremoved from the reactor under hydrogen pressure via an internal diptube and through a filter in closed communication with the reactor.Filtering under hydrogen pressure allows removal of any nickel particleswithout nickel dissolution.

Solid product is recovered by evaporation of water. The product purityis approximately 85-90%. Sorbitol is the major impurity at about 10%.The product can be used as is or purified to greater than 99%.

Step 2: Amidation

Preparation of CH₃ (CH₂)₈ C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₂ -- CH₂(CHOH)₄ CH₂ OH!NC(O)(CH₂)₈ CH₃

102.13 g of the disugar diamine product of Step 1 (0.263 moles) isdissolved in a solvent mixture of 295.16 g of water and 272.35 g ofacetone. With good mixing, 110.32 g of decanoyl chloride (0.578 moles)is slowly added (approx. 1 drop/second) to the disugar diamine solutionwhile simultaneously adding 10 wt % NaOH solution to maintain pH 9-11throughout the reaction. Once all decanoyl chloride is added, the pH isadjusted to approximately 10 and the reaction is mixed for one hour.

Solid, crude product is obtained by evaporation of water and acetone.The solid, crude product is dissolved in ethanol and the solutionfiltered to remove NaCl. The filtrate is then concentrated to obtainsolid, salt free, crude product. The product purity is approximately80-90%. The crude product can be used as is.

EXAMPLE II

Step 1: Reductive Amination

Preparation of HN CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₃ --O--(CH₂)₂ --O--(CH₂)₃ --CH₂ (CHOH)₄ CH₂ OH!NH:

1,2-Bis(3-aminopropoxy)ethane and glucose are reacted in the same manneras Step 1 of Example I for Reductive amination to produce the disugardiamine product.

Step 2: Amidation

Preparation of CH₃ (CH₂)₆ C(O)N CH₂ (CHOH)₄ CH₂ OH!--(CH₂)₃ --O--(CH₂)₂--O--(CH₂)₃ -- CH₂ (CHOH)₄ CH₂ OH!NC(O)(CH₂)₆ CH₃

312.12 g of the disugar diamine product of Step 1 (0.618 moles) ismelted under nitrogen and then dehydrated under vacuum. With goodmixing, 27.35 g of propylene glycol and 234.92 g of methyl octanoate(1.48 moles), which are preheated to 130 deg. C, are added to the melteddiamine. The reaction temperature is adjusted to 130 deg. C and 14.0 gof 25 wt % sodium methoxide (0.0618 moles) solution in methanol isadded. Once reaction is homogeneous, the temperature is dropped to90-100 deg. C and the reaction methanol is refluxed for 1-2 hours. Afterrefluxing, the methanol is distilled out with the last remainingmethanol being pulled out under vacuum for two hours. The reaction mixis poured out and allowed to cool to room temperature.

The crude product is a viscous liquid with a purity of 70-80% which canbe used as is or purified by column chromatography.

Examples 1-4

The following compositions in accord with the invention were prepared.

    ______________________________________                  % By Weight of the Total Composition                  1      2       3       4    ______________________________________    C12-C14 alkyl ethoxy sulphate                    9.30     9.30    15    9.30    C12 alkyl N-methyl glucamide                    7        4       --    7    C12-C14 alkyl carboxylate                    1        --      3.5   3.5    C12-C14 alkyl dimethyl betain                    --       1.55    2     1.55    C12/14 dimethyl amine oxide                    4        1.16    5     1.16    C16 dimethyl amine oxide                    3.9      7.75    5     --    Amide (from Ex. II)                    3.9      3.9     5     7.75    C11 alkyl ethoxylate (av. 9)                    1.0      6.0     4     3.5    Ca++            0.14     0.14    --    0.3    Mg++            0.47     0.47    0.6   0.3    Sodium cumene sulphonate                    3.7      3.7     3.7   --    EtOH            6        7       5     6    ______________________________________

What is claimed is:
 1. A liquid dishwashing detergent compositioncomprising:a) from 0.1% to 30%, by weight of the composition, of abridged polyhydroxy fatty acid amide according to the formula: ##STR12##wherein X is selected from the group consisting of substituted orunsubstituted, branched or linear alkyl, ether alkyl, amino alkyl, andamido alkyl moieties having from 2 to 15 carbon atoms; Z and Z' are thesame or different alcohol-containing moieties having two or morehydroxyl groups, or one of Z or Z' is hydrogen; and R and R' are thesame or different hydrocarbyl moieties having from 1 to 13 carbon atomsand can be saturated, branched or unsaturated or mixtures thereof; andb) a co-surfactant selected from the group consisting of C₁₆ to C₁₈amine oxides, C₁₂ -C₁₄ alkyl dimethyl betaines, alkylcarboxylates, C₁₀-C₁₈ N-alkyl polyhydroxy fatty acid amides, and mixtures thereof.
 2. Aliquid dishwashing detergent composition according to claim 1, whereinin component (a), Z and Z' are independently selected from the groupconsisting of polyhydroxyhydrocarbyl moieties having a linearhydrocarbyl chain with at least 2 hydroxyl groups directly connected tothe chain.
 3. A liquid dishwashing detergent composition according toclaim 1 wherein X is selected from the group consisting ofunsubstituted, linear alkyl moieties having the formula --(CH₂)_(n) --,wherein n is an integer from 2 to 15, unsubstituted, branched alkylmoieties having from 3 to 15 carbon atoms, unsubstituted, branched orlinear ether alkyl moieties having the formula --R² --(O--R²)_(m) --,wherein each R² is independently selected from C₂ -C₈ branched or linearalkyl or aryl moieties and m is an integer from 1 to about 5, andunsubstituted, branched or linear amino or amido alkyl moieties havingthe formula --R² --(N(R³)--R²)_(m) --, wherein each R² is independentlyselected from the group consisting of C₂ --C₈ branched, linear alkyl andaryl moieties, m is an integer from 1 to about 5, R³ is selected fromthe group consisting of hydrogen, C₁ --C₅ alkyl, and --C(O)R⁴⁻, whereinR⁴ is C₁ --C₂₁, alkyl; Z and Z' are independently selected from thegroup consisting of --CH₂ --(CHOH)_(p) --CH₂ OH --CH₂ --(CHOH)--_(p)--CH₂ OH!, --CH(CH₂ OH)--(CHOH)_(p-1) --CH₂ OH, and --CH₂ --(CHOH)₂(CHOR¹)(CHOH)--CH₂ OH, where p is an integer from 1 to 5, inclusive, andR¹ is H or a cyclic mono- or polysaccharide, and alkoxylated derivativesthereof; and R and R' are independently selected from the groupconsisting of straight or branched chain C₃ -C₁₃ alkyl or alkenylmoieties.
 4. A liquid dishwashing detergent composition according toclaim 2, wherein X is selected from the group consisting of --(CH₂)₂ --,--(CH₂)₃ --, --(CH₂)₄ --, --(CH₂)₅ --, --(CH₂)₆ --, --CH₂ CH(CH₃)(CH₂)₃--, --(CH₂)₂ --O--(CH₂)₂ --, --(CH₂)₃ --O--(CH₂)₃ --, --(CH₂)₂--O--(CH₂)₃ --, --(CH₂)₂ --O--(CH₂)₂ --O--(CH₂)₂ --, --(CH₂)₃--O--(CH₂)₂ --O--(CH₂)₃ --, --(CH₂)₂ --O--(CH₂)₃ --O--(CH₂)₂ --,--(CH₂)₂ --NH--(CH₂)₂ --, --(CH₂)₃ --NH--(CH₂)₃ --, --(CH₂)₂--NH--(CH₂)₃ --, --(CH₂)₂ --N(C(O)R)--(CH₂)₂ --, --(CH₂)₃--N(C(O)R)--(CH₂)₃ --, --(CH₂)₂ --N(C(O)R)--(CH₂)₃ --, --(CH₂)₂ --NH(C₆H₄)NH--(CH₂)₂ --, --(CH₂)₃ --NH(C₆ H₄)NH--(CH₂)₃ --, --(CH₂)₂ --NHCH₂(C₆ H₄)CH₂ NH--(CH₂)₃ --, and --(CH₂)_(2-NHCH) ₂ (C₆ H₄)CH₂ NH--(CH₂)₃--;Z and Z' are independently selected from the group consisting of--CH₂ --(CHOH)₄₋ CH₂ OH; and R and R' are independently selected fromthe group consisting of straight chain C₅ -C₁₁ alkyl and alkenylmoieties.
 5. A liquid dishwashing detergent composition according toclaim 1, comprising from 0.5% to 20% by weight of said bridgedpolyhydroxy fatty acid amide compound (a).
 6. A liquid dishwashingcomposition according to claim 5, comprising from 1% to 40% by weight ofsaid co-surfactant (b) or mixtures thereof.
 7. A liquid dishwashingdetergent composition according to claim 6, wherein said co-surfactant(b) is a C₁₆ amine oxide.
 8. A liquid dishwashing detergent compositionaccording to claim 1, wherein the pH of the composition at 20° C. is inthe range of from 3 to
 5. 9. A liquid dishwashing detergent compositionaccording to claim 1, further comprising, by weight, from 0.01% to 3% byweight calcium ions and from 0.05% to 10% by weight of a calciumstabilizing system selected from the group consisting of malic acid,malic acid salt, maleic acid, maleic acid salt, acetic acid, acetic acidsalt, and mixtures thereof.
 10. A liquid dishwashing detergentcomposition according to claim 1, wherein the alkylcarboxylate isselected from the group consisting of:i) R⁵ --R⁶ --COOMwherein R⁵ is aC₇₋₁₀ alkyl or C₇₋₁₀ alkenyl and R⁶ is benzene, cyclopentane orcylcohexane; ii) R⁷ CH(R⁸)COOMwherein R⁷ is CH₃ (CH₂)_(x) and R⁸ is CH₃(CH₂)_(y) wherein x is an integer from 4 to 10, y can be 0 or an integerfrom 1 to 4, and the sum of (x+y) is from 6 to 14; iii) CH₃ (CHR⁹)_(k)--(CH₂)_(m) --(CHR⁹)_(n) --CH(COOM)(CHR⁹)_(o) --(CH₂)_(p) --(CHR⁹)_(q)--CH₃ wherein each R⁹ is C₁₋₄ alkyl and k, n, o and q are integers inthe range of 0 to 8, provided that the total number of carbon atoms isin the range of 10 to 18; and iv) mixtures thereof.
 11. A liquiddishwashing detergent composition comprising, by weight:from 0.05% to10% of a calcium stabilizing system selected from the group consistingof malic acid, malic acid salt, maleic acid, maleic acid salt, aceticacid, acetic acid salt, and mixtures thereof; and at least 1% of asurfactant system comprising:a) a bridged polyhydroxy fatty acid amideaccording to the formula: ##STR13## wherein X is selected from the groupconsisting of substituted or unsubstituted, branched or linear alkyl,ether alkyl, amino alkyl, and amido alkyl moieties having from 2 to 15carbon atoms; Z and Z' are the same or different alcohol-containingmoieties having two or more hydroxyl groups, or one of Z or Z' ishydrogen; and R and R' are the same or different hydrocarbyl moietieshaving from 1 to 13 carbon atoms and can be saturated, branched orunsaturated or mixtures thereof; and b) a co-surfactant selected fromthe group consisting of C₁₆ to C₁₈ amine oxides, C₁₀ -C₁₆ branched alkylcarboxylates, C₆ -C₁₈ betaines, and nonbridged polyhydroxyfatty acidamides according to the formula: ##STR14## wherein R₁ is H, a C₁ -C₈hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or mixtures thereof, R₂is a C₁ -C₂₁ hydrocarbyl and Z is a polyhydrocarbyl having a linearhydrocarbyl chain with at least 2 hydroxyl groups directly connected tothe chain or an alkoxylated derivative thereof and mixtures thereof. 12.A liquid dishwashing detergent composition according to claim 11,further comprising from 0.01% to 3% calcium ions.
 13. A liquiddishwashing detergent composition according to claim 11, wherein the pHof the composition at 20° C. is in the range of from 3 to 6.5.
 14. Aliquid dishwashing detergent composition according to claim 12, furthercomprising from 0.01% to 3% magnesium ions.
 15. A liquid dishwashingdetergent composition according to claim 11, wherein the weight ratio ofsaid bridged polyhydroxy fatty acid amide (a) to said co-surfactant (b)is from 1:50 to 50:1.
 16. A liquid dishwashing detergent compositioncomprising at least 1%, by weight, of a surfactant system comprising:a)a bridged polyhydroxy fatty acid amide according to the formula:##STR15## wherein X is selected from the group consisting of substitutedor unsubstituted, branched or linear alkyl, ether alkyl, amino alkyl,and amido alkyl moieties having from 2 to 15 carbon atoms; Z and Z' arethe same or different alcohol-containing moieties having two or morehydroxyl groups, or one of Z or Z' is hydrogen; and R and R' are thesame or different hydrocarbyl moieties having from 1 to 13 carbon atomsand can be saturated, branched or unsaturated or mixtures thereof; b) aco-surfactant selected from the group consisting of C₁₆ to C₁₈ amineoxides, C₁₀ -C₁₈ branched alkyl carboxylates, C₆ -C₁₈ betaines, andnonbridged polyhydroxyfatty acid amides according to the formula:##STR16## wherein R₁ is H, a C₁ --C₈ hydrocarbyl, 2-hydroxy ethyl,2-hydroxy propyl or mixtures thereof, R₂ is a C₁ --C₂₁ hydrocarbyl and Zis a polyhydrocarbyl having a linear hydrocarbyl chain with at least 2hydroxyl groups directly connected to the chain or an alkoxylatedderivative thereof and mixtures thereof;wherein the pH of thecomposition at 20° C. is in the range of from 3 to 6.5.
 17. A liquiddishwashing detergent composition according to claim 16, furthercomprising an alkyl amphocarboxylic acid of the formula: ##STR17##wherein R' is a C₈₋₁₈ alkyl group and Ri has the formula: ##STR18##wherein R¹⁰ is a (CH₂)_(x) COOM or CH₂ CH₂ OH, x is 1 or 2, and M is analkali metal, alkaline earth metal, ammonium, monoethanolammonium,diethanolammonium, or triethanolammonium.
 18. A liquid dishwashingdetergent composition according to claim 16 comprising:a) from 0.1% to30%, by weight, of the bridged polyhydroxy fatty acid amide; and b) from1% to 40%, by weight, of the co-surfactant;wherein the ratio of bridgedpolyhydroxy fatty acid amide to co-surfactant is in a ratio of from 1:50to 50:1 and the pH of the composition at 20° C. is in the range of from3 to
 5. 19. A liquid dishwashing detergent composition according toclaim 16, wherein said co-surfactant (b) is a non bridged polyhydroxyfatty acid amide wherein R₂ is a C₁₀ -C₁₈ alkyl group.